CN102483574A - Radiation-sensitive resin composition and compound - Google Patents

Radiation-sensitive resin composition and compound Download PDF

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CN102483574A
CN102483574A CN201080040708XA CN201080040708A CN102483574A CN 102483574 A CN102483574 A CN 102483574A CN 201080040708X A CN201080040708X A CN 201080040708XA CN 201080040708 A CN201080040708 A CN 201080040708A CN 102483574 A CN102483574 A CN 102483574A
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CN102483574B (en
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中原一雄
佐藤光央
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

Abstract

Disclosed are: a radiation-sensitive resin composition which fulfils both exposure latitude and MEEF performance,and a compound which can be used suitably in the radiation-sensitive resin composition. The radiation-sensitive resin composition comprises: (A) a compound having such a structure that a group represented by formula (1) is bound to a nitrogen atom,(B) a resin which has an acid-dissociative solubility-suppressing group and of which the alkali solubility can be increased by the action of an acid,and (C) a radiation-sensitive acid-generating agent.

Description

Radiation sensitive resin composition and compound
Technical field
The present invention relates to the radiation sensitive resin composition that uses in the manufacturing, other photoengraving operation of the circuit substrate of semiconductor manufacturing process, liquid crystal, thermal head (thermal head) etc. and the compound that is suitable as the constituent of this radiation sensitive resin composition at IC etc.More specifically, relate to the radiation sensitive resin composition that can be adapted at the chemical amplification type that uses in the far ultraviolet below the wavelength 250nm of KrF PRK, ArF PRK etc., the photoengraving operation that electron beam is exposure light source.
Background technology
The radiation sensitive resin composition of chemical amplification type is the exposure portion that the is radiated at production acid through the far ultraviolet that is representative, electron beam with KrF PRK, ArF PRK; Through being that the chemical reaction of catalyzer makes exposure portion and unexposed the dissolution velocity in developer solution produce difference with this acid, on substrate, form the composition of resist pattern.
As can with short wavelength more carry out microfabrication, be the photoetching material of light source with the ArF PRK, what for example use is not have the polymkeric substance of the ester ring type hydrocarbon of big absorption in the 193nm zone in skeleton, to have, especially in its repetitive, have the resin combination of the polymkeric substance of lactone skeleton as constituent.
In order to obtain technology stability, in above-mentioned radiation sensitive resin composition, add nitrogen-containing compound (with reference to patent documentation 1～3).In addition, in order to improve the lithography performance of isolated patterns, also studied and added nitrogen compound (with reference to patent documentation 4,5) with specific carbamate groups.
Patent documentation
Patent documentation 1: japanese kokai publication hei 5-232706 communique
Patent documentation 2: japanese kokai publication hei 5-249683 communique
Patent documentation 3: japanese kokai publication hei 5-158239 communique
Patent documentation 4: TOHKEMY 2001-166476 communique
Patent documentation 5: TOHKEMY 2001-215689 communique
Summary of the invention
But, the miniaturization of resist pattern proceeded to below the live width 90nm level now, not only need the raising of the such fundamental characteristics of the raising of rectangularity of expansion and pattern of raising, focal length of exploring degree, also need other performance.For example, at present, as one of miniaturization technology of resist pattern, immersion exposure has obtained practicability, thereby needs to tackle the anticorrosive additive material of this immersion exposure.Particularly, need develop and satisfy the material that requires characteristic as the reduction of the MEEF (mask error enhancer, Mask Error Enhancement Factor) of the index of expression mask error permission etc.
The present invention is based on above situation and accomplish; Its purpose is to provide the fundamental characteristics that not only satisfies sensitivity, resolution etc., also satisfies the radiation sensitive resin composition of exposure latitude and MEEF performance and is suitable for the compound of this radiation sensitive resin composition.
The invention of accomplishing in order to solve above-mentioned problem is a radiation sensitive resin composition, it is characterized in that, contains:
(A) have the compound (following also abbreviate as " compound (A) ") of the structure that the group (below be also referred to as " group (1) ") of following formula (1) expression combines with nitrogen-atoms,
(B) have resin (following also abbreviate as " resin (B) ") that acid dissociation property dissolution inhibiting group and the effect alkali-soluble through acid increase and
(C) radiation-sensitive acid producing agent (below be also referred to as " acid producing agent (C) ").
(in the formula (1), Y is for by following formula (i) expression and carbon number being 5～20 1 valency group." * " representes the binding site (combining hand) with nitrogen-atoms.)
Figure BDA0000142942810000022
(in the formula (i), R 1, R 2And R 3Be straight chain shape or the alkyl of branched or 1 valency ester ring type alkyl, the perhaps R of carbon number 4～12 of carbon number 1～4 independently of one another 1And R 2Mutually combining and forming carbon number with the carbon atom that they combined is 4～12 divalent ester ring type alkyl.The binding site of " * " expression oxygen atom.)
In this radiation sensitive resin composition, compound (A) is preferably the compound (below be also referred to as " compound (A-1) ") of following formula (1-1) expression.
Figure BDA0000142942810000031
(in the formula (1-1), the definition of Y is identical with following formula (1).R 4And R 5Be alkyl, 1 valency ester ring type alkyl, aryl or aralkyl, the perhaps R of hydrogen atom, straight chain shape or branched independently of one another 4And R 5Mutually combining and forming carbon number with the nitrogen-atoms that they combined is 4～20 divalent hetero ring type group.)
In this radiation sensitive resin composition, the Y in the following formula (1) is preferably tertiary pentyl.
In this radiation sensitive resin composition, resin (B) preferably has the repetitive (below be also referred to as " repetitive (3) ") of following formula (3) expression.
Figure BDA0000142942810000032
(in the formula (3), R is hydrogen atom or methyl.R 6, R 7And R 8Be straight chain shape or the alkyl of branched or 1 valency ester ring type alkyl, the perhaps R of carbon number 4～20 of carbon number 1～4 independently of one another 6, R 7And R 8In 2 to mutually combine and form carbon number with the carbon atom that they combined be 4～20 divalent ester ring type alkyl.)
In this radiation sensitive resin composition, (B) resin preferably has the repetitive that contains at least a skeleton of from lactone skeleton and cyclic carbonate skeleton, selecting.
Compound of the present invention is to have the structure that the group of following formula (I) expression combines with nitrogen-atoms, and molecular weight is the compound (below be also referred to as " compound (A-I) ") below 3,000.
Figure BDA0000142942810000041
(in the formula (I), the binding site of " * " expression and nitrogen-atoms.)
As above-claimed cpd, be preferably the compound of following formula (I-1) expression.
Figure BDA0000142942810000042
(in the formula (I-1), R 4And R 5Be alkyl, 1 valency ester ring type alkyl, aryl or aralkyl, the perhaps R of hydrogen atom, straight chain shape or branched independently of one another 4And R 5Mutually combining and forming carbon number with the nitrogen-atoms that they combined is 4～20 divalent hetero ring type group.)
Utilize radiation sensitive resin composition of the present invention, not only sensitivity and excellent in resolution can be provided but also satisfy exposure latitude and the material of the chemical amplification type anti-corrosion agent of MEEF performance.Utilize compound of the present invention, can access not only sensitivity and excellent in resolution but also satisfy exposure latitude and the radiation sensitive resin composition of MEEF performance.
Embodiment
Below the mode to embodiment of the present invention describes, but the present invention is not limited to following embodiment.
< radiation sensitive resin composition >
Radiation sensitive resin composition of the present invention contains compound (A), resin (B) and acid producing agent (C), can also further contain any composition.This radiation sensitive resin composition is through also containing the compound (A) with above-mentioned ad hoc structure on the basis of containing resin (B) and acid producing agent (C), thereby makes the lithography performance of the resist that obtains excellent, especially exposure latitude and MEEF excellence.Below each constituent is described successively.
< compound (A) >
Compound among the present invention (A) is for having the compound of the structure that group (1) combines with nitrogen-atoms.Particularly; Can enumerate with group (1) replace the hydrogen atom combines with nitrogen-atoms more than 1 and must compound, said nitrogen-atoms is the nitrogen-atoms in the compound that has more than 1 amino of at least 1 hydrogen atom and nitrogen-atoms be combined into (below be also referred to as " amino-compound (a) ").Above-mentioned amino-compound (a) can have more than 2 the amino of at least 1 hydrogen atom and nitrogen-atoms be combined into.At this moment, can use group (1) to replace 1 in the hydrogen atom of above-mentioned amino, also can use group (1) to replace a plurality of hydrogen atoms.In addition, can use group (1) to replace 1 hydrogen atom in the amino of 1 nitrogen-atoms and the hydrogen atom be combined into more than 2, also can use group (1) to replace a plurality of hydrogen atoms.Under above-mentioned situation, the Y in a part in the group of a plurality of existence (1) can be identical separately or different.
Compound (A) forms the amino compound of alkalescence for the effect through acid is dissociated group (1), have the effect of the lithography performance of the resist that raising makes by radiation sensitive resin composition of the present invention.Compare its more remarkable effect with the amines that gets with tertbutyloxycarbonyl replacement hydrogen atom in the past.Think this be through with replacing amines that hydrogen atom get with tertbutyloxycarbonyl and compare and make the carbon number change that breaks away from group many in the past; Thereby the disengaging ability that breaks away from group improves; The control transfiguration of the alkalescence in the resist film is prone to; And the transpiration from the material of the disengaging group in the resist film the during postexposure bake (PEB) when being suppressed at the prebake conditions (PB) before the exposure, after the exposure, therefore further improve lithography performance.Thinking that the disengaging ability of above-mentioned disengaging group exists with ... is considered to the cationic stability that the effect through acid produces.
Group (1) is the specific ester group of following formula (1) expression, it is characterized by Y representes in following formula (1) carbon number 5～20, preferably the alkyl of the acid dissociation property of carbon number 5～13 combines with the end of-COO-structure.As above-mentioned Y, through being made as the alkyl of carbon number 5～20, thereby can make because of dissociating of causing of acid is easy to take place, the control transfiguration of the alkalescence in the resist film is prone to, lithography performance is improved.And, also have the such effect of sublimability that can suppress compound (A).
As the R in the following formula (i) of expression Y 1, R 2And R 3The straight chain shape of the carbon number 1～4 of expression or the alkyl of branched can be enumerated methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl etc.As R 1, R 2And R 31 valency ester ring type alkyl and R of the carbon number 4～12 of expression 1And R 2The divalent ester ring type alkyl of the carbon number 4～12 that mutually combines and form with the carbon atom that they combined can be enumerated the group from the cycloalkane of cyclo-butane, cyclopentane, cyclohexane, cyclooctane, cyclodecane etc.; Group from the bridging alicyclic ring same clan of norcamphane, tristane, Fourth Ring decane, diamantane etc.
As the 1 valency group that the Y in the following formula (1) representes, be preferably tertiary pentyl, 1-ethyl-1-methyl-propyl, 1, the branched-chain alkyl of 1-diethyl propyl group etc.; Group with alicyclic structure of following formula (i-1)～(i-15) expression.Wherein, be easy to synthetic aspect more preferably tertiary pentyl.
Figure BDA0000142942810000061
As amino-compound (a), for example can enumerate following formula (2) expression compound (below be also referred to as " amino-compound (a1) ", with the compound that has 2 nitrogen-atoms in a part (below be also referred to as " amino-compound (a2) "), compound (below be also referred to as " amino-compound (a3) "), the compound that contains amide group, carbamide compound, nitrogen-containing heterocycle compound etc. with 3 above nitrogen-atoms.
Figure BDA0000142942810000071
In following formula (2), R 4And R 5Definition identical with following formula (1-1), can be alkyl, 1 valency ester ring type alkyl, aryl or aralkyl, the perhaps R of hydrogen atom, straight chain shape or branched independently of one another 4And R 5Mutually combine and form the divalent hetero ring type group of carbon number 4～20 with the nitrogen-atoms that they combined.
As R 4And R 5The straight chain shape of expression or the alkyl of branched are preferably the group of carbon number more than 4, can enumerate normal-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc.As 1 valency ester ring type alkyl, can enumerate cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group, norcamphane base, three ring decyls, Fourth Ring dodecyl, adamantyl etc.As aryl, can enumerate phenyl, naphthyl etc.In addition, aralkyl is meant with the substituted low alkyl group of aryl, particularly, can enumerate benzyl, phenylethyl, phenyl propyl, naphthyl methyl, naphthyl ethyl etc.As R 4And R 5The divalent hetero ring type group of the carbon number 4～20 that mutually combines and form with the nitrogen-atoms that they combined can be enumerated the group of the structure with pyrroles, imidazoles, pyrazoles, pyrrolidine, piperidines, piperazine, morpholine etc.Should explain; Part or all of the hydrogen atom that above-mentioned group had can use hydroxyl, carboxyl ,-the COOR base ,-replacements such as OCOR base (above-mentioned R is the alkyl of carbon number 1～10), cyanic acid; Especially if replace the part of the hydrogen atom that above-mentioned group has with hydroxyl; Then can further suppress the distillation of the compound (A) in the heat treated, thus preferred.
As amino-compound (a1), for example can enumerate the monoalkyl amine of n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, cyclohexylamine etc.; The dialkyl amine of di-n-butylamine, two n-amylamines, two n-hexylamines, two positive heptyl amices, two n-octyl amines, two positive nonyl amines, two n-Decylamines, cyclohexyl-methyl amine, dicyclohexyl amine etc.; Aniline, methylphenylamine, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 2, the aromatic amine of 6-diisopropyl aniline, 4-nitroaniline, diphenylamine, naphthalidine, 2-(4-aminophenyl)-2-(3-hydroxyphenyl) propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl) propane etc.; The alkanol amine of monoethanolamine, diethanolamine etc.; The 1-diamantane amine of 1-amantadine, N-methyl isophthalic acid-amantadine etc.
As amino-compound (a2), for example can enumerate 1,2-diaminoethanes, 1,4-diaminobutane, 1; 6-diamino hexane, 1,7-diamido heptane, 1,8-diamido octane, 1; 9-diamido nonane, 1,10-diamino decane, 1,12-diamido dodecane, 4; 4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminobenzophenone, 2; Two (4-aminophenyl) propane of 2-, 2-(3-aminophenyl)-2-(4-aminophenyl) propane, 1, two [1-(4-the aminophenyl)-1-Methylethyl] benzene, 1 of 4-, two [1-(4-aminophenyl)-1-Methylethyl] benzene of 3-etc.As amino-compound (a3), for example can enumerate 4,4 '-diamino-diphenylamine, PAH, gather the polymkeric substance of methallyl amine, N-(2-amino-ethyl) acrylic amide etc.
As the above-mentioned compound that contains amide group, for example can enumerate formamide, N-NMF, acetamide, N-methylacetamide, propionamide, benzamide, pyrrolidone etc.As above-mentioned carbamide compound, for example can enumerate urea, methyl urea, 1,1-dimethyl urea, 1,3-dimethyl urea, 1,3-diphenyl urea, three normal-butyl thiocarbamides etc.As above-mentioned nitrogen-containing heterocycle compound, for example can enumerate the imidazoles of imidazoles, benzimidazole, glyoxal ethyline, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, 2-methyl-4-phenylimidazole, 2-tolimidazole, 2-Phenylbenzimidazole etc., in addition; Also can enumerate indoles, pyrroles, pyrazoles, adenine, guanine, purine, pyrrolidine, 2-pyrrolidine carbinol, 3-pyrrolidinol, piperidines, morpholine, 4-hydroxy piperidine, 2,6-lupetidine, 4-hydroxyl-2,6-lupetidine, 2; 2,6,6-tetramethyl piperidine, 4-hydroxyl-2; 2; 6,6-tetramethyl piperidine, piperazine, high piperazine, 1-methyl piperazine, 1-ethyl piperazidine, 2-methyl piperazine, 1-isopropyl piperazine, 1-piperazine ethanol, 2,5-lupetazin, 2; 6-lupetazin, 3-amino-pyrrolidine, L-proline, 4-hydroxyl-L-proline, pipecoliacid, nipecotic acid, isonipecotic acid, 2-piperazine carboxylic acid, 1; 4,7-7-triazacyclononane, 1,4; 7,10-tetraazacyclododecanand etc.
In above-mentioned amino-compound (a), preferred amino-compound (a1), amino-compound (a2) and nitrogen-containing heterocycle compound.In addition, in amino-compound (a1), further preferred dialkyl amine, 1-diamantane amine, preferred especially two n-octyl amines, two positive nonyl amines, two n-Decylamines, dicyclohexyl amine, 1-amantadine, N-methyl isophthalic acid-amantadine.In amino-compound (a2), further preferred 1,6-diamino hexane, 1,7-diamido heptane, 1,8-diamido octane, 1,9-diamido nonane, 1,10-diamino decane, 1,12-diamido dodecane, 4,4 '-diaminodiphenyl-methane.In nitrogen-containing heterocycle compound; Further preferred pyrrolidine, piperidines, imidazoles; Preferred especially pyrrolidine, 2-pyrrolidine carbinol, 3-pyrrolidinol, piperidines, 4-hydroxy piperidine, 4-hydroxyl-2,6-lupetidine, 4-hydroxyl-2,2; 6,6-tetramethyl piperidine, L-proline, 4-hydroxyl-L-proline, benzimidazole, glyoxal ethyline, 2-Phenylbenzimidazole.In addition, the pKa of the conjugate acid of amino-compound (a) (measure 25 ℃ of temperature, below identical) is preferably more than 0.At this moment, if the pKa that uses such conjugate acid such as amide compound for example replaces amino-compound (a) less than 0 compound, then there are the exploring degree of the resist that infringement obtains, the situation of pattern form.
The molecular weight of compound (A) is generally 100～3, and 000, be preferably 150～2,000, be preferably 200～1,000 especially.Compound (A) can use separately or mix more than 2 kinds and use.
In this radiation sensitive resin composition,, can enumerate compound of the present invention (A-I) with structure that uncle's penta oxygen carbonyl combines with nitrogen-atoms as preferred especially compound (A).If concrete expression then can be enumerated uncle's N-penta oxygen carbonyl di-n-octyl amine, uncle's N-penta oxygen carbonyl two n-nonyl amine, uncle's N-penta oxygen carbonyl two positive decyl amine, uncle's N-penta oxygen carbonyl dicyclohexyl amine, uncle's N-penta oxygen carbonyl-1-amantadine, uncle's N-penta oxygen carbonyl-N-methyl isophthalic acid-amantadine, N, N-two (uncle's penta oxygen carbonyl)-1-amantadine, uncle's N-penta oxygen carbonyl-N-methyl isophthalic acid-amantadine, N; N '-two (uncle's penta oxygen carbonyl)-4,4 '-diaminodiphenyl-methane, N, N '-two (uncle's penta oxygen carbonyl)-1; 6-diamino hexane, N, N, N ' N '-four (uncle's penta oxygen carbonyl)-1; 6-diamino hexane, N, N '-two (uncle's penta oxygen carbonyl)-1,7-diamido heptane, N; N '-two (uncle's penta oxygen carbonyl)-1; 8-diamido octane, N, N '-two (uncle's penta oxygen carbonyl)-1,9-diamido nonane, N; N '-two (uncle's penta oxygen carbonyl)-1; 10-diamino decane, N, N '-two (uncle's penta oxygen carbonyl)-1,12-diamido dodecane, uncle's N-penta oxygen carbonyl-pyrrolidine, uncle's N-penta oxygen carbonyl-2-pyrrolidine carbinol, uncle's N-penta oxygen carbonyl-3-pyrrolidinol, uncle's N-penta oxygen carbonyl-piperidines, uncle's N-penta oxygen carbonyl-4-hydroxy piperidine, uncle's N-penta oxygen carbonyl-4-hydroxyl-2; 6-lupetidine, uncle's N-penta oxygen carbonyl-4-hydroxyl-2; 2,6,6-tetramethyl piperidine, uncle's N-penta oxygen carbonyl-L-proline, uncle's N-penta oxygen carbonyl-4-hydroxyl-L-proline, uncle's N-penta oxygen carbonyl benzimidazole, uncle's N-penta oxygen carbonyl-2-tolimidazole, uncle's N-penta oxygen carbonyl-2-Phenylbenzimidazole etc.
The synthetic method of compound (A) is described below.
Can be through after amino-compound (a) and alkali (below be also referred to as " alkali (b) ") being added in the solvent (below be also referred to as " solvent (s) "); Add Y-OCO-O-COO-Y (wherein; The Y of Y and following formula (1) is equivalent in meaning) two carbonate compounds or the E-COO-Y of expression are (wherein; The Y of Y and following formula (1) is equivalent in meaning, and E representes any in fluorine atom, chlorine atom, bromine atoms and the iodine atom) expression the halo carboxylic acid compounds and synthesize.Should explain, according to circumstances, also can not use alkali (b) or solvent (s).
After the reaction, as required, can be refining through distillation, recrystallization, column chromatography, liquid-liquid cleaning, solid-liquid cleaning etc., obtain compound (A) then.
As alkali (b); Can use trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, diisopropylethylamine, diisopropylamine, dicyclohexyl amine, 1-methyl piperidine, 1-crassitude, quinuclidine, 1; 4-diazabicyclo [2.2.2] octane, 1; 8-diazabicyclo [5.4.0] 11-7-alkene, pyridine, 4-picoline, 2; 6-lutidines, 2; 6-diisopropyl pyridine, 2,6-di-tert-butyl pyridine, lithium hydroxide, NaOH, potassium hydroxide, sodium carbonate, sal tartari, soda mint, saleratus, lithium, sodium, potassium, lithium hydride, sodium hydride, hydrofining, calcium hydride, diisopropyl amide lithium, n-BuLi, s-butyl lithium, tert-butyl lithium, sodium tert-butoxide, potassium tert-butoxide etc.As alkali (b), can use separately or mix more than 2 kinds and use.
As solvent (s), can use heptane, hexane, Anaesthetie Ether, methylene chloride, chloroform, tetrahydrofuran, ethyl acetate, dimethyl formamide, dimethyl acetamide, two
Figure BDA0000142942810000101
alkane, acetone, methyl ethyl ketone, methyl isobutyl ketone, water etc.As solvent (s), can use separately or mix more than 2 kinds and use.
Use the synthetic of above-mentioned two carbonate compounds can be with reference to Journal of Medicinal Chemistry 1998, Vol.41, p.4983-4994 etc.
As using the synthetic of above-mentioned halo carboxylic acid compounds, be the chlorine atomic time for example at E, that is, when using the chloro-carbonic acid compound, can be synthetic according to following process flow diagram.As required, in each reaction, can use alkali (b), solvent (s).
Figure BDA0000142942810000102
In the following formula, the definition of Y is identical with Y in the following formula (1).1eq is meant 1 equivalent.
In this radiation sensitive resin composition, can also and not use other the nitrogen-containing compound such as amino-compound (a), tertiary amine compound, quaternary ammonium hydroxide of group (1) protection to mix and use compound (A).
As tertiary amine compound, for example can enumerate three (ring) alkyl amine of triethylamine, Tri-n-Propylamine, tri-n-butylamine etc.; N, the aromatic amine of accelerine etc.; Triethanolamine, N, the alkanol amine of N-two (hydroxyethyl) aniline etc.; N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N '-four (2-hydroxypropyl) ethylenediamine, two (2-dimethyl aminoethyl) ether, two (2-diethylamino ethyl) ether etc.
As quaternary ammonium hydroxide, for example can enumerate four n-pro-pyl ammonium hydroxide, 4-n-butyl ammonium hydroxide etc.
With respect to resin (B) 100 mass parts, be preferably 0.01～10 mass parts as the content of the compound in this radiation sensitive resin composition (A), more preferably 0.1～5 mass parts further is preferably 0.3～3 mass parts.Content through making compound (A) can further improve the exposure latitude and the MEEF performance of the radiation sensitive resin composition that obtains in above-mentioned scope.
< resin (B) >
In the present invention, the resin (wherein, do not comprise compound (A)) of resin (B) for having acid dissociation property dissolution inhibiting group and increasing through sour effect alkali-soluble.Resin (B) is the insoluble or alkali slightly solubility of alkali before the acid effect.At this; So-called " the insoluble or alkali slightly solubility of alkali " be meant that usefulness under the alkaline development condition that when utilizing the resist tunicle is formed by this radiation sensitive resin composition to form the resist pattern, is adopted is only used resin (B) and must tunicle replace above-mentioned resist tunicle and when developing, in the character more than 50% of the initial stage of remaining this tunicle after development thickness.
As resin (B), as long as the resin for having acid dissociation property dissolution inhibiting group and increasing through sour effect alkali-soluble does not just have special qualification.As above-mentioned acid dissociation property dissolution inhibiting group, as long as, just do not have special qualification for dissociating and the group that increases of the alkali-soluble of resin (B) thus through the effect of acid.
Resin (B) preferably has repetitive (3) as the repetitive that contains acid dissociation property dissolution inhibiting group.
As repetitive (3), the repetitive of preferred especially following formula (3-1)～(3-18) expression.Resin (B) can contain a kind of above-mentioned repetitive separately or contain more than 2 kinds.
Figure BDA0000142942810000121
In the following formula (3-1)～(3-18), the definition of R is identical with following formula (3).
In resin (B), the containing ratio of repetitive (3) is preferably 5～80 moles of % with respect to the whole repetitives that constitute resin (B), and more preferably 10～80 moles of % are preferably 20～70% especially.If the containing ratio of repetitive (3) surpasses 80 moles of %, then exist the adaptation of resist film to reduce the possibility that pattern collapse, pattern peel off.
Resin (B) preferably has and contains from by the repetitive of at least a kind of skeleton selecting lactone skeleton and the cyclic carbonate skeleton (below be also referred to as " repetitive (4) ").
As above-mentioned repetitive (4), can enumerate the repetitive of following formula (4-1)～(4-5) expression as the repetitive that contains the lactone skeleton, and can enumerate the repetitive of following formula (4-6) expression as the repetitive that contains the cyclic carbonate skeleton.
Figure BDA0000142942810000131
In the following formula (4-1)～(4-6), R is hydrogen atom or methyl.R 9Be hydrogen atom or methyl.R 10Be hydrogen atom or methoxyl.X is singly-bound or methylene.Z is methylene or oxygen atom.N and m are 0 or 1.
As the repetitive of following formula (4-1) expression, the repetitive that is preferably following formula (4-1-1) and (4-1-2) representes.As the repetitive of following formula (4-2) expression, be preferably the repetitive of following formula (4-2-1) expression.As the repetitive of following formula (4-3) expression, be preferably the repetitive of following formula (4-3-1) expression.As the repetitive of following formula (4-4) expression, be preferably the repetitive of following formula (4-4-1) expression.As the repetitive of following formula (4-5) expression, be preferably the repetitive of following formula (4-5-1) expression.
Figure BDA0000142942810000141
Following formula (4-1-1), (4-1-2), (4-2-1), (4-3-1), (4-4-1) and (4-5-1) in, R is hydrogen atom or methyl.
In resin (B), with respect to the whole repetitives that constitute resin (B), the containing ratio of repetitive (4) is that the total amount of repetitive (4) is preferably 0～70 mole of %, further is preferably 20～60 moles of %.Through reaching such containing ratio, can improve development property as resist, defective, low LWR, low PEB temperature dependency etc.On the other hand, if surpass 70 moles of %, then there are the exploring degree as resist, the possibility that LWR reduces.
In addition, resin (B) can contain the repetitive with functional group that following formula representes.
In the following formula, R is hydrogen atom or methyl.
And then resin (B) can contain from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-two ring [2.2.1] heptyl ester, (methyl) acrylic acid-two ring [4.4.0] ester in the last of the ten Heavenly stems, (methyl) acrylic acid-two ring [2.2.2] monooctyl ester, (methyl) acrylic acid-three ring [5.2.1.0 2,6] last of the ten Heavenly stems ester, (methyl) acrylic acid-diamantane ester, (methyl) acrylic acid-three ring [3.3.1.1 3,7] last of the ten Heavenly stems (methyl) acrylic ester such as ester repetitive.
The conventional method synthetic resin (B) of free radical polymerization capable of using etc.For example, preferably utilize drips of solution that monomer and radical initiator will be contained in (1) to be added to reaction dissolvent perhaps to contain in the solution of monomer and make it carry out the method for polyreaction; The solution that (2) will contain monomer is added drop-wise to reaction dissolvent respectively with the solution that contains radical initiator or contains in the solution of monomer and makes it carry out the method for polyreaction; The multiple solution that (3) will contain various monomers is added drop-wise to reaction dissolvent respectively with the solution that contains radical initiator or contains the method for its method of carrying out polyreaction etc. is synthesized.
Should explain; As far as monomer solution, when the dropping monomer solution made its reaction, the amount of monomer in the monomer solution of dropping was preferably 30 moles more than the % with respect to the employed monomer total amount of polymerization; More preferably 50 moles more than the %, be preferably 70 moles especially more than the %.
Temperature of reaction in the said method can suitably be confirmed according to initiator type.Be generally 30～180 ℃, be preferably 40～160 ℃, further be preferably 50～140 ℃.The dropping time is according to the condition of the kind of temperature of reaction, initiating agent, the monomer of reaction etc. and difference, but be generally 30 minutes～8 hours, be preferably 45 minutes～6 hours, further be preferably 1～5 hour.In addition, the total reaction time that comprises the dropping time also with the dropping time likewise according to condition and different, be generally 30 minutes～8 hours, be preferably 45 minutes～7 hours, further be preferably 1～6 hour.
As the radical initiator that in above-mentioned polymerization, uses, can enumerate 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), 2,2 '-azo two (2-cyclopropyl propionitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile) etc.These initiating agents can use separately or mix more than 2 kinds and use.
As polymer solvent, be the solvent that hinders polymerization (have polymerization-inhibiting effects nitrobenzene, have the sulfhydryl compound of chain transfer effect etc.) in addition solvent, as long as, just can use for dissolving the solvent of this monomer.For example, can enumerate alcohols, ethers, ketone, amide-type, ester lactone, nitrile and mixed solvent thereof etc.These solvents can use separately or mix more than 2 kinds and use.
The resin that gets through polyreaction preferably reclaims through reprecipitation method.That is, after polyreaction finishes, through polymer fluid is put in the precipitation solvent again, and reclaim the target resin with the form of powder.As precipitation solvent again, can use separately as above-mentioned polymer solvent and illustrative solvent or mix more than 2 kinds and use.Except reprecipitation method, can also remove low molecular compositions such as monomer, oligomer through the separatory operation, reclaim resin.Promptly; After polyreaction finishes; Suitably concentrate polymeric solution, for example optionally add the dicyandiamide solution that is separated into two kinds of liquid of methyl alcohol/heptane etc., from resin solution, remove low molecular composition; Be replaced into suitable required dicyandiamide solution (propylene glycol monomethyl ether etc.), with the form recovery target resin of solution.
Should explain that resin (B) contains the low molecular weight compositions from monomer, its containing ratio is preferably below the 0.1 quality % with respect to the total amount 100 quality % of resin (B), further is preferably below the 0.07 quality %, is preferably especially below the 0.05 quality %.
At the containing ratio of this low molecular weight compositions is 0.1 quality % when following, uses this resin (B) to make resist film, when carrying out immersion exposure, can make to water that resist film contacts in the quantitative change of leachable of stripping few.And then when the keeping resist, the situation of in resist, separating out foreign matter is few, even when resist applies, it is also few that irregular situation takes place to apply.Thereby, the generation of the defective in the time of can suppressing the formation of resist pattern fully.
Should explain, in this manual, when " low molecular weight compositions " that is called from monomer, be meant that the weight-average molecular weight by polystyrene conversion (following be designated as sometimes " Mw ") of utilizing gel permeation chromatography (GPC) to record is the composition below 500.Particularly, be compositions such as monomer, dimer, tripolymer, oligomer.This low molecular weight compositions for example can pass through the chemical refining method of washing, liquid-liquid extraction etc., combination such as the physics method for refining of chemical refining method and ultrafiltration, centrifuging etc. and method etc. remove.
In addition, this low molecular weight compositions can be through the analysis that utilizes high performance liquid chromatography (HPLC) for resin (B) quantitatively.Should explain that the impurity of the low molecular weight compositions of preferred resin (B) and halogen, metal etc. is few more good more, thus, the sensitivity in the time of can further improving as resist, exploring degree, technology stability, pattern form etc.
On the other hand, the weight-average molecular weight by polystyrene conversion that gel permeation chromatography (GPC) records (below be designated as " Mw ") of utilizing of resin (B) does not have special qualification, is preferably 1,000～100; 000, further be preferably 1,000～30,000; Be preferably 1,000～20,000 especially.The Mw deficiency of resin (B) 1,000 o'clock, the trend that the thermotolerance when existing as resist reduces.On the other hand, if the Mw of resin (B) surpasses 100,000, the trend of the development property reduction when then existing as resist.
In addition, the Mw of resin (B) with utilize the number-average molecular weight that gel permeation chromatography (GPC) records by polystyrene conversion (below be designated as " Mn ".) ratio (Mw/Mn) be generally 1.0～5.0, be preferably 1.0～3.0, further be preferably 1.0～2.0.
In radiation sensitive resin composition of the present invention, can use resin (B) separately, perhaps mix more than 2 kinds and use.
< acid producing agent (C) >
As the acid producing agent among the present invention (C), preferably contain the compound of following formula (C-1) expression.
Figure BDA0000142942810000181
In the following formula (C-1), R 11Be the alkyl of hydrogen atom, fluorine atom, hydroxyl, carbon number 1～10, the alkoxy of carbon number 1～10 or the alkoxy carbonyl group of carbon number 2～11.R 12Be the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10 or the alkane sulfonyl of carbon number 1～10.R 13And R 14Can be alkyl, phenyl or the naphthyl of carbon number 1～10, perhaps R independently of one another 13And R 14Mutually combine and form the divalent group of carbon number 2～10.K is 0～2 integer.R is 0～10 integer.X -Negative ion for following formula (c-1)～(c-4) expression.
R 15C pH qF rSO 3 -：(c-1)
R 15SO 3 -：(c-2)
Among following formula (c-1), (c-2), R 15The alkyl that perhaps can contain substituent carbon number 1～12 for hydrogen atom, fluorine atom.P is 1～10 integer, and q and r are the integer and r ≠ 0 of satisfying 2p=q+r.
Figure BDA0000142942810000182
In the following formula (c-3), R 16And R 17Be the fluorine substituted alkyl of carbon number 1～10 independently of one another.R 16And R 17Can mutually combine and form the divalent fluorine substituted alkylene of carbon number 2～10.
Figure BDA0000142942810000191
In the following formula (c-4), R 18, R 19And R 20Be the fluorine substituted alkyl of carbon number 1～10 independently of one another.R 18, R 19And R 20In 2 can mutually combine and form the divalent fluorine substituted alkylene of carbon numbers 2～10.
As the R in the following formula (C-1) 11～R 14The alkyl of carbon number 1～10 of expression except the example of the alkyl of above-mentioned carbon number 1～4, also can be enumerated straight chain shape alkyl such as n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl; Branched-chain alkyls such as neopentyl, 2-ethylhexyl etc.Wherein, be preferably methyl, ethyl, normal-butyl, the tert-butyl group.
In addition, as R 11And R 12The alkoxy of the carbon number 1～10 of expression can be enumerated straight chain shape alkoxys such as methoxyl, ethoxy, positive propoxy, n-butoxy, just own oxygen base, branched alkoxys such as isopropoxy, dissident's oxygen base etc.Wherein, be preferably methoxyl, ethoxy, positive propoxy, n-butoxy.
In addition, as R 11The alkoxy carbonyl group of the carbon number 2～11 of expression can be enumerated straight chain shape alkoxy carbonyl groups such as methoxycarbonyl group, carbethoxyl group, positive butoxy carbonyl, just own oxygen carbonyl, branched alkoxy carbonyl groups such as the different third oxygen carbonyl, dissident's oxygen carbonyl etc.Wherein, be preferably methoxycarbonyl group, carbethoxyl group, positive butoxy carbonyl.
In addition, as R 12The alkane sulfonyl of the carbon number 1～10 of expression; Can enumerate straight chain shape alkane sulfonyls such as methane sulfonyl, ethane sulfonyl, n-propane sulfonyl, normal butane sulfonyl, normal hexane sulfonyl; Branched alkane sulfonyls such as isobutane sulfonyl, isohexane sulfonyl, cycloalkanes sulfonyls such as cyclopentane sulfonyl, cyclohexane sulfonyl, cyclooctane sulfonyl etc.Wherein, be preferably methane sulfonyl, ethane sulfonyl, n-propane sulfonyl, normal butane sulfonyl, cyclopentane sulfonyl, cyclohexane sulfonyl.
In addition, in following formula (C-1), r is preferably 0～2 integer.
In the following formula (C-1), as R 13And R 14The aryl of expression except phenyl, also can be enumerated o-tolyl, a tolyl, p-methylphenyl, 2, substituted-phenyls such as 3-xylyl; With part or all of the hydrogen atom of these groups use at least a kind of group from hydroxyl, carboxyl, cyanic acid, nitro, alkoxy, alkoxyalkyl, alkoxy carbonyl group and alkoxy-carbonyl oxy, selecting to replace and group etc.
Carry out in the substituted group at hydrogen atom,, can enumerate straight chain shape alkoxys such as methoxyl, ethoxy, positive propoxy, n-butoxy as alkoxy to above-mentioned phenyl or substituted-phenyl; Branched alkoxys such as isopropoxy, 2-methyl propoxyl group, 1-methyl propoxyl group, tert-butoxy; Cycloalkyloxy such as cyclopentyloxy, cyclohexyloxy etc.The carbon number of these groups is preferably 1～20.
As above-mentioned alkoxyalkyl, can enumerate straight chain shape alkoxyalkyls such as methoxy, ethoxyl methyl, 2-methoxy ethyl, 2-ethoxyethyl group; Branched alkoxyalkyls such as 1-methoxy ethyl, 1-ethoxyethyl group; In addition, also can enumerate alkoxyalkyl with naphthenic hydrocarbon structure etc.The carbon number of these groups is preferably 1～20.
As above-mentioned alkoxy carbonyl group, can enumerate straight chain shape alkoxy carbonyl groups such as methoxycarbonyl group, carbethoxyl group, the positive third oxygen carbonyl, positive butoxy carbonyl; Branched alkoxy carbonyl groups such as the different third oxygen carbonyl, 2-methyl-prop oxygen carbonyl, 1-methyl-prop oxygen carbonyl, tertbutyloxycarbonyl; Encircle cycloalkoxycarbonyls such as penta oxygen carbonyl, hexamethylene oxygen carbonyl etc.The carbon number of these groups is preferably 2～21.
As above-mentioned alkoxy-carbonyl oxy, can enumerate straight chain shape alkoxy-carbonyl oxies such as methoxycarbonyl oxygen base, ethoxy carbonyl oxygen base, positive propoxy ketonic oxygen base, n-butoxy ketonic oxygen base; Branched alkoxy-carbonyl oxies such as isopropoxy carbonyl oxygen base, tert-butoxycarbonyl oxygen base; Cyclo alkoxy carbonyl oxygen bases such as cyclopentyloxy ketonic oxygen base, cyclohexyloxy carbonyl oxygen base etc.The carbon number of these groups is preferably 2～21.
As R 13And R 14The aryl of expression is preferably phenyl, 4-cyclohexyl phenyl, 4-tert-butyl-phenyl, 4-methoxyphenyl, 4-tert-butoxy phenyl.
In addition, as R 13And R 14The naphthyl of expression for example except that the 1-naphthyl, also can be enumerated substituted naphthyls such as 2-methyl isophthalic acid-naphthyl, 3-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl; With part or all of the hydrogen atom of these groups use at least a kind of group from hydroxyl, carboxyl, cyanic acid, nitro, alkoxy, alkoxyalkyl, alkoxy carbonyl group and alkoxy-carbonyl oxy, selecting to replace and group etc.
Hydrogen atom as to naphthyl or substituted naphthyl carries out substituted alkoxy, alkoxyalkyl, alkoxy carbonyl group, alkoxy-carbonyl oxy, can enumerate illustrative group of above-mentioned phenyl.
As R 13And R 14The naphthyl of expression is preferably 1-naphthyl, 1-(4-methoxyl naphthyl), 1-(4-ethoxy naphthyl), 1-(4-positive propoxy naphthyl), 1-(4-n-butoxy naphthyl), 2-(7-methoxyl naphthyl), 2-(7-ethoxy naphthyl), 2-(7-positive propoxy naphthyl), 2-(7-n-butoxy naphthyl).
In addition, as R 13And R 14The mutually combine divalent group of the carbon number 2～10 that forms is preferably R 13And R 14Form 5 yuan of rings or the group of 6 yuan of rings, especially form the group of 5 yuan of rings (thiophane ring) with the sulphur atom that they combined.
Part or all of the hydrogen atom of above-mentioned divalent group can use a kind of group from hydroxyl, carboxyl, cyanic acid, nitro, alkoxy, alkoxyalkyl, alkoxy carbonyl group and alkoxy-carbonyl oxy, selecting to replace.As alkoxy, alkoxyalkyl, alkoxy carbonyl group, alkoxy-carbonyl oxy, can enumerate illustrative group of above-mentioned phenyl.
As R 13And R 14, be preferably methyl, ethyl, phenyl, 4-methoxyphenyl, 1-naphthyl, and R 13And R 14Mutually combine and form the group of thiophane ring with the sulphur atom that they combined.
The above formula (C-1) represented by the acid generator (C) of the cation, preferably triphenyl sulfonium cation, tri -1 - naphthyl sulfonium cation, tri - t-butylphenyl sulfonium cation 4 - fluoro- phenyl - diphenyl sulfonium cation, di-4 - fluorophenyl - phenyl sulfonium cation, tri -4 - fluorophenyl sulfonium cation 4 - cyclohexyl-phenyl - diphenyl sulfonium cation 4 - methanesulfonyl- phenyl - diphenyl sulfonium cation 4 - cyclohexane sulfonyl - diphenyl sulfonium cation, 1 - naphthyl-dimethyl sulfonium cation, 1 - naphthyl diethyl sulfonium cation, 1 - (4 - hydroxy-naphthalene yl) dimethyl sulfonium cation, 1 - (4 - methyl-naphthyl) dimethyl sulfonium cation, 1 - (4 - methyl-naphthyl) diethyl sulfonium cation, 1 - (4 - cyano-naphthyl) dimethyl sulfonium cation, 1 - (4 - cyano-naphthyl) sulfonium cation diethyl 1 - (3,5 - dimethyl-4 - hydroxyphenyl) tetrahydrothiophene
Figure BDA0000142942810000211
cation, 1 - (4 - A oxy naphthyl) tetrahydrothiophene
Figure BDA0000142942810000212
cation, 1 - (4 - ethoxy-naphthyl) tetrahydrothiophene
Figure BDA0000142942810000213
cation, 1 - (4 - n-propoxy naphthyl) tetrahydrothiophene
Figure BDA0000142942810000214
cation, 1 - (4 - n-butyl oxy naphthyl) tetrahydrothiophene
Figure BDA0000142942810000215
cation, 2 - (7 - methoxy-naphthyl) tetrahydrothiophene
Figure BDA0000142942810000216
cationic 2 - (7 - ethoxynaphthyl) tetrahydrothiophene
Figure BDA0000142942810000217
cationic 2 - (7 - n-propoxy Base naphthyl) tetrahydrothiophene
Figure BDA0000142942810000218
cation, 2 - (7 - n-butoxy naphthyl) tetrahydrothiophene
Figure BDA0000142942810000219
cation.
In the following formula (c-1) ,-C pH qF r-be the fluorine alkylidene of carbon number p, can be straight chain shape or branched.P is preferably 1,2,4 or 8, and r is preferably the integer more than 2.In addition, q can be 0.
Following formula (c-1) and (c-2) in, as R 15The alkyl of carbon number 1～12 of expression is preferably alkyl, naphthenic base or the bridging ester ring type alkyl of carbon number 1～12.
Following formula (c-3) and (c-4) in, as R 16～R 20The fluorine substituted alkyl of the carbon number 1～10 of expression can be enumerated trifluoromethyl, pentafluoroethyl group, seven fluoropropyls, nine fluorine butyl, ten difluoro amyl groups, perfluoro capryl etc.
As R in following formula (c-3) 16And R 17Mutually combine form and in following formula (c-4) R 18～R 20In the divalent fluorine substituted alkylene of 2 carbon numbers 2～10 of forming of mutually combining, can enumerate tetrafluoro ethylidene, hexafluoro propylidene, octafluoro butylidene, ten fluorine pentylidene, 11 fluorine hexylidenes etc.
As the negative ion in the acid producing agent (C) of following formula (C-1) expression; Be preferably trifluoro-methanyl sulfonate negative ion, perfluor-normal butane sulfonate anionic, perfluor-normal octane sulfonate anionic, 2-(dicyclo [2.2.1] heptan-2-yl)-1; 1; 2,2-HFC-134a sulfonate anionic, 2-(dicyclo [2.2.1] heptan-2-yl)-1,1-Difluoroethane sulfonate anionic, 1-adamantyl sulfonate anionic; In addition, also be preferably following formula (c-1-1) and (c-1-2) and the negative ion of following formula (c-3-1)～(c-3-7) expression.
Figure BDA0000142942810000221
Figure BDA0000142942810000231
Acid producing agent (C) for example can be by above-mentioned illustrative kation and anionic constituting.Wherein, this combination does not have special qualification.In this radiation sensitive resin composition, acid producing agent (C) can use a kind separately, perhaps mixes more than 2 kinds and uses.
As acid producing agent (C); Except the acid producing agent of above-mentioned (C-1) expression, for example also can enumerate salt compound, halogen-containing compound, diazo-ketones compound, sulphones, sulfoacid compound etc.Particularly, can enumerate following compound.
As salt compound, for example can enumerate iodine
Figure BDA0000142942810000234
salt, sulfonium salt,
Figure BDA0000142942810000235
salt, diazonium
Figure BDA0000142942810000236
salt, pyridine
Figure BDA0000142942810000237
salt etc.
As halogen-containing compound, for example can enumerate the hydrocarbon compound of haloalkyl containing, the hetero ring type compound of haloalkyl containing etc.
As the diazo-ketones compound, for example can enumerate 1,3-diketo-2-diazo-compounds, diazobenzene naphtoquinone compounds, diazo naphthoquinone compound etc.
As sulphones, for example can enumerate the α-diazo-compounds of beta-keto sulfone, 'Beta '-sulfonyl sulfone, above-claimed cpd etc.
As sulfoacid compound, for example can enumerate alkyl sulfonic ester, alkyl sulfonic acid acid imide, haloalkyl sulphonic acid ester, aromatic yl sulphonate, imino group sulphonic acid ester etc.
These acid producing agents (C) can use a kind separately, perhaps mix more than 2 kinds and use.
In this radiation sensitive resin composition, total use amount of acid producing agent (C) is seen as the sensitivity of resist and the viewpoint of development property from guaranteeing, with respect to resin (B) 100 mass parts, is generally 0.1～30 mass parts, is preferably 0.5～20 mass parts.During total use amount less than 0.1 mass parts, there is the trend of sensitivity and the reduction of development property.On the other hand,, then exist the transparency to reduce, be difficult to obtain the trend of the resist pattern of rectangle radioactive ray if surpass 30 mass parts.In addition, the usage ratio of the acid producing agent beyond the acid producing agent of above-mentioned (C-1) expression is preferably below the 80 quality % with respect to acid producing agent (C) total amount, further is preferably below the 60 quality %.
< solvent (D) >
Radiation sensitive resin composition of the present invention contains solvent (D) usually.The solvent that uses does not just have special qualification as long as be the solvent of dissolved compound (A), resin (B) and acid producing agent (C) at least and the adjuvant (E) that adds as required.
For example, can use alcohols, ethers, ketone, amide-type, ester lactone, nitrile and mixed solvent thereof etc.
Wherein, be preferably the propylene-glycol monoalky lether acetate esters, be preferably propylene glycol methyl ether acetate especially.In addition, be preferably ketone, 2 hydroxy propanoic acid alkyl esters, 3-alkoxypropan acid alkyl ester class and gamma-butyrolacton.These solvents can use a kind separately, perhaps mix more than 2 kinds and use.
< adjuvant (E) >
Can in this radiation sensitive resin composition, cooperate various adjuvants (E) such as fluorine resin, ester ring type framework compound, surfactant, sensitizer as required.Can suitably confirm the use level of each adjuvant according to purpose.
Fluorine resin shows in immersion exposure that especially the resist film face of sening as an envoy to reveals the effect of water proofing property.And it is the composition with following effect, that is, even thereby suppress composition from resist film to the effect of liquid immersion liquid stripping, or have and carry out the also not residual drop of immersion exposure through high-velocity scanning and suppress watermark defective etc. is soaked the defective that causes by liquid effect.
The structure of fluorine resin does not have special qualification, can enumerate (1) himself in developer solution insoluble and through the effect of acid become alkali-soluble fluorine resin, (2) himself in developer solution solvable and fluorine resin that effect alkali-soluble through acid increases, (3) himself is insoluble and become himself effect alkali-soluble solvable and through alkali increases in developer solution fluorine resin of fluorine resin, (4) etc. of alkali-soluble through the effect of alkali in developer solution.
As fluorine resin, can enumerate polymkeric substance with fluorine-containing repetitive.Be preferably the polymkeric substance that further has above-mentioned repetitive (3).
As above-mentioned fluorine-containing repetitive, for example can enumerate from trifluoromethyl (methyl) acrylic ester, 2,2 repetitive of 2-trifluoroethyl (methyl) acrylic ester, perfluor ethyl (methyl) acrylic ester etc.
As fluorine resin, for example preferably contain the combination of polymers of the repetitive of following formula (Ea)～(Ef) expression.These fluorine resins can use a kind perhaps to mix use more than 2 kinds separately.
Figure BDA0000142942810000261
In the following formula (Ea)～(Ef), R ' is hydrogen atom or methyl.
The ester ring type framework compound be demonstrate further improve dry ecthing patience, pattern form, with the composition of the effect of the cementability of substrate etc.
As the ester ring type framework compound, for example can enumerate the adamantane derivative class of 1-adamantanecarboxylic acid, 2-diamantane ketone, the 1-adamantanecarboxylic acid tert-butyl ester etc.; The deoxycholate class of the deoxycholic acid tert-butyl ester, deoxycholic acid tertbutyloxycarbonyl methyl esters, deoxycholic acid 2-ethoxy ethyl ester etc.; The lithocholate class of the lithocholic acid tert-butyl ester, lithocholic acid tertbutyloxycarbonyl methyl esters, lithocholic acid 2-ethoxy ethyl ester etc.;
3-[2-hydroxyl-2, two (trifluoromethyl) ethyls of 2-] Fourth Ring [4.4.0.1 2,5.1 7,10] dodecane, 2-hydroxyl-9-methoxycarbonyl-5-oxo-4-oxa--three ring [4.2.1.0 3,7] nonane etc.These ester ring type framework compounds can use a kind perhaps to mix use more than 2 kinds separately.
Surfactant is the composition that demonstrates the effect of improvement screening characteristics, striped, development property etc.As surfactant; For example can enumerate nonionics such as polyoxyethylene lauryl ether, the hard ester group ether of polyoxyethylene, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, polyethylene glycol dilaurate, polyglycol distearate is surfactant; In addition, can enumerate KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), POLYFLOW NO.75, POLYFLOW NO.95 (chemical company of common prosperity society system), EFTOPEF301, EFTOP EF303, EFTOP EF352 (TochemProducts corporate system), Megafac F171, Megafac F173 (big Japanese ink chemical industrial company system), FlorardFC430, Florard FC431 (Sumitomo 3M corporate system), Asahi Guard AG710, SurflonS-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (Asahi Glass corporate system) etc. as trade name below.These surfactants can use a kind perhaps to mix use more than 2 kinds separately.
Sensitizer is to demonstrate the energy of absorption radioactive ray and also increase the material of the effect of sour growing amount thus for acid producing agent (C) this energy delivery, has the effect of " the apparent sensitivity " of this radiation sensitive resin composition of raising.
As sensitizer, can enumerate that carbazoles, acetophenones, benzophenone, naphthalene class, phenols, diacetyl, dawn are red, rose-red, pyrene class, anthracene class, phenothiazines etc.These sensitizers can use a kind perhaps to mix use more than 2 kinds separately.
As adjuvant (E), can also use dyestuff, pigment, bonding auxiliary agent etc.For example, can make the sub-image of exposure portion visual, the influence of the halation in the time of can relaxing exposure through using dyestuff or pigment.In addition, through cooperating bonding auxiliary agent, can improve cementability with substrate.In addition, as adjuvant (E), except that above-mentioned, also can enumerate alkali soluble resin, have low molecular alkali dissolution property controlling agent, antihalation agent, preserving stabilizer, foam-breaking agent of acid dissociation property blocking group etc.
Should explain that adjuvant (E) can use the various adjuvants of having explained more than a kind separately, also can be also with more than 2 kinds.
< preparation method of radiation sensitive resin composition >
When using radiation sensitive resin composition of the present invention; Usually through it being dissolved in the solvent (D) so that the total solid constituent concentration reaches 1～50 quality %, preferably reaches 2～25 quality %; For example filter then, thereby be prepared into composition solution with the filtrator about the 0.2 μ m of aperture.
< the formation method of photoresist pattern >
Radiation sensitive resin composition of the present invention is as the chemical amplification type anti-corrosion agent and useful.In the chemical amplification type anti-corrosion agent, through utilizing the effect of the acid that exposure produces by acid producing agent (C), the resinous principle that dissociates, main dissociate acid dissociation property dissolution inhibiting group in the resin (B), thus produce carboxyl etc.As a result, the dissolubility of exposure portion in alkaline-based developer of resist uprises, this exposure portion by alkaline-based developer dissolving, remove, obtain the photoresist pattern of eurymeric etc.
As photoresist pattern formation method, for example being commonly is described below forms the photoresist method of patterning.That is, utilize this radiation sensitive resin composition after forming photoresist film on the substrate (operation (1)) through (1); (2) photoresist film (as required be situated between by liquid soak medium) the irradiation radioactive ray of mask to forming through having predetermined pattern are with its exposure (operation (2)); Heated substrates (through the photoresist film of exposure) (operation (3)); Develop (operation (4)) (4) then, thereby can form the photoresist pattern.
In operation (1); Through utilizing suitable coating method such as spin coated, curtain coating coating, roller coat with radiation sensitive resin composition or it is dissolved in the composition solution that get in the solvent is coated on the substrate (silicon chip, with the thin slice of silicon dioxide, antireflection film covering etc.), thus the formation photoresist film.Particularly, the application of resin composition solution makes the solvent evaporates in filming through prebake conditions (PB) then so that the resist film that obtains reaches the thickness of regulation, forms resist film.
In operation (2),, make its exposure to the photoresist film that in operation (1), forms (liquid that according to circumstances is situated between by water etc. soaks medium) irradiation radioactive ray.Should explain that this moment is through having the mask irradiation radioactive ray of predetermined pattern.As radioactive ray,, can be suitably from visible light, ultraviolet ray, far ultraviolet, X ray, charged particle line etc., select and shine according to the live width of target pattern.Being preferably with ArF PRK (wavelength 193nm), KrF PRK (wavelength 248nm) is the far ultraviolet of representative, wherein, is preferably the ArF PRK.
Operation (3) be called as postexposure bake (PEB), in operation (2) acid that in the part of exposure, produces of photoresist film by acid producing agent with the operation of resin deprotections such as (B).Make the part (exposure portion) of exposure produce difference with the dissolubility of unexposed part (unexposed portion) in alkaline-based developer.PEB implements through in 50 ℃～180 ℃ scope, suitably selecting.
In operation (4), through will be through the photoresist film development of exposure, thereby form the photoresist pattern of regulation with developer solution.After the development, water cleans, carries out drying usually.As developer solution; For example be preferably and be dissolved with NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl-diethyl-amine, ethyl dimethylamine, triethanolamine, TMAH, pyrroles, piperidines, choline, 1; 8-diazabicyclo [5.4.0]-7-undecylene, 1, at least a kind alkaline aqueous solution in 5-diazabicyclo [4.3.0]-alkali compounds such as 5-nonene.
In addition, preceding in operation (2) when carrying out immersion exposure, contact with the direct of resist film in order to protect the liquid immersion liquid, the insoluble liquid of liquid immersion liquid can be set on resist film soak and use diaphragm.Soak as liquid and to use diaphragm, can use in the exfoliated diaphragm of peeling off simultaneously at the exfoliated diaphragm of the preceding solvent that utilizes solvent to peel off of operation (4) (for example with reference to TOHKEMY 2006-227632 communique), with the development of operation (4) of developer solution (for example with reference to WO2005-069076 communique, WO2006-035790 communique) any.Wherein, see, preferably use the exfoliated liquid of developer solution to soak and use diaphragm from the viewpoint of turnout.
Embodiment
Below enumerate embodiment, further embodiment of the present invention is specified.But the present invention does not receive any restriction of these embodiment.In present embodiment and comparative example, " part " short of special record is a quality criteria just.Various mensuration in embodiment and comparative example are carried out according to following method.
[polystyrene conversion weight-average molecular weight (Mw), polystyrene conversion number-average molecular weight (Mn)]
Mw and Mn are through using eastern Cao's corporate system GPC post (2 of G2000HXL, 1 of G3000HXL, 1 of G4000HXL); Under the analysis condition of 40 ℃ of flow 1.0 ml/min, eluting solvent tetrahydrofuran, column temperature, through being that the gel permeation chromatography (GPC) of standard is measured with single dispersion polyethylene.
[ 1H-NMR analyzes]
Compound (A) 1H-NMR analyzes and uses nuclear magnetic resonance device (trade name: JNM-ECX400, NEC's corporate system) to measure.
[ 13C-NMR analyzes]:
Each polymkeric substance 13C-NMR analyzes and uses nuclear magnetic resonance device (trade name: JNM-ECX400, NEC's corporate system) to measure.
< synthesizing of compound (A) >
[embodiment 1] (synthesizing of compound (A-1))
Preparation coke acid two tert-pentyl ester 5g are dissolved among the methylene chloride 5mL and solution.In the there-necked flask of the 100mL that has thermometer and tap funnel, add 4-hydroxy piperidine 1.87g, triethylamine 3.73g, methylene chloride 20mL, in ice bath, stirred 15 minutes.Use tap funnel wherein to drip preprepared coke acid two tert-pentyl ester solution with 5 fens clockwise.After dripping end, further in ice bath, stirred 30 minutes, then, from ice bath, take out, at room temperature stirred 7 hours, finish reaction.
Reaction drops into reaction solution after finishing in separating funnel, add the acetic acid aqueous solution 50mL of 1.0 moles/L, after stirring tempestuously, obtains oil reservoir.And then, according to identical order, handle the oil reservoir of obtaining with acetic acid aqueous solution, the oil reservoir that obtains is cleaned with saturated sodium bicarbonate aqueous solution 100mL.Then, obtain oil reservoir, carry out drying to wherein adding anhydrous magnesium sulfate.After the oil reservoir drying, low boiling point component is heated up in a steamer in decompression, separates uncle's N-penta oxygen carbonyl-4-hydroxy piperidine (compound (A-1)) (3.1g, yield 77%) through silica gel column chromatography.
1The result that H-NMR analyzes: the chemical shift of compound (A-1) is as follows.
1H-NMR(CDCl 3)：δ3.85(3H)、3.03(2H)、1.85(2H)、1.76(2H)、1.43(8H)、0.89(3H)
< synthesizing of resin (B) >
Resin (B-1)～(B-3) as resin (B) uses the monomer of following formula (M-1)～(M-6) expression synthetic in each synthetic example.
(M-1): methacrylic acid 1-methyl ring pentyl ester
(M-2): methacrylic acid 1-ethyl diamantane ester
(M-3): methacrylic acid 4-oxa--5-oxo three ring [4.2.1.0 3,7] nonane-2-base ester
(M-4): methacrylic acid 1-ethyl ring pentyl ester
(M-5): methacrylic acid 1-isopropyl ring pentyl ester
(M-6): methacrylic acid 1,3-dioxa-2-oxo-cyclopentane-4-base methyl esters
Figure BDA0000142942810000311
[synthetic example 1] (synthesizing of resin (B-1))
Preparation is dissolved in monomer (M-1) 14.20g (35 moles of %), monomer (M-2) 8.99g (15 moles of %) and monomer (M-3) 26.81g (50 moles of %) among the 2-butanone 100g and further drops into 2, two (2 Methylpropionic acid methyl esters) 2.78g of 2 '-azo as initiating agent and monomer solution.
Then, 2-butanone 50g is put in the there-necked flask of the 500mL that has thermometer and tap funnel, carry out 30 minutes nitrogen purgings.Behind the nitrogen purging, in flask,, be heated to 80 ℃ with in the magnetic stirrer.Use tap funnel with dripping preprepared monomer solution in 3 hours.Dropping is begun as polymerization cause the time, implemented polyreaction 6 hours.After the finishing polymerization, polymeric solution is cooled to below 30 ℃ through water-cooled.After the cooling, put into 1, in the hexane of 000g, filter and take out the white powder of being separated out.Be dissolved into once more in the 2-butanone of 200g filtering the white powder that takes out, put into 1 then, in the hexane of 000g, filter and take out the white powder of being separated out.And then, carry out identical operations once more.Then, the white powder that filtration is obtained descended dry 17 hours at 50 ℃, obtained the multipolymer (38g, yield 75%) of white powder.With this multipolymer as resin (B-1).
The Mw of this multipolymer is 6,520, and Mw/Mn is 1.61, 13The result that C-NMR analyzes: from monomer (M-1), the containing ratio of each repetitive of monomer (M-2) and monomer (M-3) is 35.5: 15.3: 49.2 (mole %).
[synthetic example 2] (synthesizing of resin (B-2))
Preparation monomer (M-1) 27.64g (60 moles of %), monomer (M-6) 10.19g (20 moles of %) and monomer (M-3) 12.17g (20 moles of %) are dissolved among the 2-butanone 100g and further drop into dimethyl azobis isobutyronitrile 2.25g as initiating agent and monomer solution.
Then, in the there-necked flask of the 500mL that has thermometer and tap funnel, drop into the 2-butanone of 50g, carry out 30 minutes nitrogen purging.Behind the nitrogen purging, in flask with being heated to 80 ℃ in the magnetic stirrer.Use tap funnel with dripping preprepared monomer solution in 3 hours.Dropping is begun as polymerization cause the time, implemented polyreaction 6 hours.After the finishing polymerization, polymeric solution is cooled to below 30 ℃ through water-cooled.After the cooling, it is put into 1, in the hexane of 000g, filter and take out the white powder of being separated out.Be dissolved into again in the 2-butanone of 200g filtering the white powder that takes out, then it put into 1, in the hexane of 000g, filter and take out the white powder of being separated out.And then, carry out identical operations once more.Then, the white powder that filtration is obtained descended dry 17 hours at 50 ℃, obtained the multipolymer (36g, yield 72%) of white powder.With this multipolymer as resin (B-2).
The Mw of this multipolymer is 6,720, and Mw/Mn is 1.52, 13The result that C-NMR analyzes: from monomer (M-1), the containing ratio of each repetitive of monomer (M-6) and monomer (M-3) is 59.1: 20.3: 20.6 (mole %).
[synthetic example 3] (synthesizing of resin (B-3))
Preparation is dissolved in monomer (M-4) 22.82g (50 moles of %), monomer (M-5) 4.92g (10 moles of %) and monomer (M-3) 22.26g (40 moles of %) among the 2-butanone 100g and further to wherein dropping into 2, two (2 Methylpropionic acid methyl esters) 1.15g of 2 '-azo as initiating agent and monomer solution.
Then, the 2-butanone of 50g is put in the there-necked flask of the 500mL that has thermometer and tap funnel, carried out 30 minutes nitrogen purging.Behind the nitrogen purging, in flask with being heated to 80 ℃ in the magnetic stirrer.Use tap funnel with dripping preprepared monomer solution in 3 hours.Dropping is begun as the polymerization start time, implemented polyreaction 6 hours.After the finishing polymerization, polymeric solution is cooled to below 30 ℃ through water-cooled.After the cooling, it is put into 1, in the hexane of 000g, filter and take out the white powder of being separated out.Be dissolved in again in the 2-butanone of 200g filtering the white powder that takes out, then it put into 1, in the hexane of 000g, filter and take out the white powder of being separated out.And then, carry out identical operations once more.Then, the white powder that filtration is obtained descended dry 17 hours at 50 ℃, obtained the multipolymer (39g, yield 78%) of white powder.With this multipolymer as resin (B-3).
The Mw of this multipolymer is 11,320, and Mw/Mn is 1.57, 13The result that C-NMR analyzes: from monomer (M-4), the containing ratio of each repetitive of monomer (M-5) and monomer (M-3) is 49.7: 9.3: 41.0 (mole %).
< synthesizing of resin (F) >
Use the compound of following formula (S-1)～(S-5) expression, the fluorine resin (resin (F)) that contains as adjuvant (E) in the radiation sensitive resin composition that uses in synthetic following embodiment and the comparative example.
[synthetic example 4] (synthesizing of polymkeric substance (F-1))
Preparation is dissolved in the monomer solution that also further drops into azobis isobutyronitrile 1.74g among the 2-butanone 100g and get with compound (S-1) 7.70g (20 moles of %) and compound (S-2) 42.30g (80 moles of %).On the other hand, in the there-necked flask of 500mL, drop into the 2-butanone of 50g, carry out 30 minutes nitrogen purging after, in stirred autoclave, be heated to 80 ℃.Then, use tap funnel with dripping preprepared monomer solution in 3 hours.To drip beginning and cause the time, implement polyreaction 6 hours as polymerization.
After the finishing polymerization, polymeric solution is cooled to below 30 ℃, this polymeric solution is moved in the separating funnel of 2L through water-cooled.With the methyl alcohol dilution polymeric solution of 150g, the hexane that drops into 600g mixes, and then, drops into the steaming of 21g and stays water further to stir, and leaves standstill 30 minutes.Then, reclaim lower floor, process propylene glycol methyl ether acetate solution.The yield of the solid constituent of propylene glycol methyl ether acetate solution (polymkeric substance) is 71%, and Mw is 6,850, and Mw/Mn is 1.38, 13The result that C-NMR analyzes: the containing ratio (mole %) from the repetitive of compound (S-1) and compound (S-2) was respectively 20.6: 79.4, and the contain fluorine atoms ratio is 12.1%.With this multipolymer as resin (F-1).
<upper layer film is synthetic with polymkeric substance >
When the pattern in following embodiment and comparative example forms, soak the composition that forms composition with the upper layer film of diaphragm with polymkeric substance as forming liquid through the synthetic following upper layer film of following method.
[synthetic example 5] (upper layer film is synthetic with polymkeric substance (1))
Prepare respectively in advance with compound (S-3) 22.26g and 2,2-azo two (2-methyl isopropyl acid methyl esters) 4.64g be dissolved among the 2-butanone 25g and monomer solution (i) and in advance compound (S-4) 27.74g is dissolved among the 2-butanone 25g and monomer solution (ii).On the other hand, 2-butanone 100g is put in the there-necked flask of the 500mL that has thermometer and tap funnel, carry out 30 minutes nitrogen purging.Behind the nitrogen purging, be heated to 80 ℃ when in flask, stirring with magnetic stirring apparatus.
Use tap funnel, drip preprepared monomer solution (i) with 20 minutes, make its slaking after 20 minutes, continue (ii) with 20 minutes dropping monomer solutions.Then, further carry out 1 hour reaction, be cooled to below 30 ℃ and obtain copolymer fluid.Behind the copolymer fluid simmer down to 150g that obtains, move in the separating funnel.In this separating funnel, drop into methyl alcohol 50g and normal hexane 400g, implement separation and purification.After the separation, reclaim subnatant.The subnatant that reclaims is replaced as 4-methyl-2-amylalcohol, forms resin solution.The Mw of the multipolymer that in the resin solution that obtains, contains is 5,730, and Mw/Mn is 1.23, and yield is 26%.In addition, be respectively 50.3: 49.7 (mole %) from the containing ratio of the repetitive of compound (S-3) and compound (S-4), it is 43.6% that fluorine atom contains proportional.With this multipolymer as upper layer film with polymkeric substance (1).
[synthetic example 6] (upper layer film is synthetic with polymkeric substance (2))
Preparation is compound (S-4) 46.95g (85 moles of %) and 2,2 '-azo is two-(2 Methylpropionic acid methyl esters) 6.91g be dissolved among the isopropyl alcohol 100g and monomer solution.On the other hand, in the there-necked flask of the 500mL that has thermometer and tap funnel, drop into isopropyl alcohol 50g, carry out 30 minutes nitrogen purging.Behind the nitrogen purging, in flask with being heated to 80 ℃ in the magnetic stirrer.Use tap funnel with dripping preprepared monomer solution in 2 hours.
After dripping end, further carry out 1 hour reaction, the aqueous isopropanol 10g with dropping in 30 minutes is dissolved with compound (S-5) 3.05g (15 moles of %) then, further carries out 1 hour reaction.Be cooled to below 30 ℃, obtain copolymer fluid.After the copolymer fluid that obtains is condensed into 150g, move in the separating funnel.In this separating funnel, drop into methyl alcohol 50g and normal hexane 600g, implement separation and purification.After the separation, reclaim subnatant.With this subnatant of isopropanol and the feasible 100g that forms, move in the separating funnel once more.Methyl alcohol 50g and normal hexane 600g are put in the separating funnel, implement separation and purification, after the separation, reclaim subnatant.The subnatant that reclaims is replaced as 4-methyl-2-amylalcohol, total amount is adjusted into 250g.After the adjustment, add entry 250g and implement separation and purification, after the separation, reclaim upper strata liquid.
The upper strata liquid that reclaims is replaced as 4-methyl-2-amylalcohol, forms resin solution.The Mw of the multipolymer that in the resin solution that obtains, contains is 9,760, and Mw/Mn is 1.51, and yield is 65%.In addition, be respectively 95.0: 5.0 (mole %) from the containing ratio of the repetitive of compound (S-4) and compound (S-5), it is 36.8% that fluorine atom contains proportional.With this multipolymer as upper layer film with polymkeric substance (2).
<upper layer film forms the preparation of composition (H) >
When the pattern in following embodiment and comparative example forms, use through the above-mentioned synthetic upper layer film that makes and use polymkeric substance, be used to form liquid through following method preparation and soak upper layer film formation composition (H) with diaphragm.
[synthetic example 7] (upper layer film forms the preparation of composition (H))
Upper layer film through being blended in preparation in the synthetic example 5 with polymkeric substance (2) 93 mass parts, diethylene glycol monoethyl ether acetic acid esters 10 mass parts, 4-methyl-2-hexanol 10 mass parts and diisoamyl ether 90 mass parts, prepares upper layer film formation composition (H) with the upper layer film of polymkeric substance (1) 7 mass parts, preparation in synthetic example 6.
< preparation of radiation sensitive resin composition >
For for each composition (compound (A) nitrogen-containing compound, acid producing agent (C) and solvent (D) in addition) of compound (A), resin (B) and resin (F) formation radiation sensitive resin composition in addition synthetic in the foregoing description and the synthetic example, as follows.
< compound (A) nitrogen-containing compound in addition >
(a-1): N-tertbutyloxycarbonyl-4-hydroxy piperidine
(a-2): 2-Phenylbenzimidazole
(a-3): 2, the 6-diisopropyl aniline
< acid producing agent (C) >
(C-1): triphenylsulfonium 2-(dicyclo [2.2.1] heptan-2-yl)-1,1-Difluoroethane sulphonate (compound of following formula (C-1) expression)
(C-2): triphenylsulfonium 2-(diamantane-1-yl)-1,1-Difluoroethane sulphonate (compound of following formula (C-2) expression)
(C-3): 4-cyclohexyl phenyl-diphenyl sulfonium nine fluoro-normal butane sulphonate (compound of following formula (C-3) expression)
(C-4): triphenylsulfonium 6-(diamantane-1-base ketonic oxygen base)-1,1,2,2-tetrafluoro hexane sulphonate (compound of following formula (C-4) expression)
< solvent (D) >
(D-1): propylene glycol methyl ether acetate
(D-2): cyclohexanone
(D-3): gamma-butyrolacton
[embodiment 2]
Mixing cpd (A-1) (uncle's N-penta oxygen carbonyl-4-hydroxy piperidine) 0.7 mass parts, resin (B-1) 100 mass parts that in synthetic example 1, make, as (C-1) of acid producing agent (C) (triphenylsulfonium 2-dicyclo [2.2.1] heptan-2-base-1; 1-Difluoroethane sulphonate) 7.5 mass parts; In this potpourri, add (D-1) propylene glycol methyl ether acetate 1 as solvent (D); 500 mass parts, (D-2) cyclohexanone 650 mass parts and (D-3) gamma-butyrolacton 30 mass parts, the dissolving said mixture obtains mixed solution; Filter the mixed solution of gained, preparation radiation sensitive resin composition with the filtrator of aperture 0.20 μ m.
[embodiment 3～5, comparative example 1～3]
The use level of each composition that constitutes radiation sensitive resin composition (with resin (B) as 100 mass parts) is become use level as shown in table 1 below, in addition, carry out 2 identical operations, the preparation radiation sensitive resin composition with embodiment.
[table 1]
Figure BDA0000142942810000381
[evaluation]
The ArF PRK as light source, is carried out the evaluation of sensitivity, EL and MEEF to the radiation sensitive resin composition that in embodiment 2～5 and comparative example 1～3, obtains.With regard to each embodiment and comparative example, in the pattern formation method (P-1)～(P-3) of following explanation, form pattern through the pattern formation method shown in the table 2, estimate.
(pattern formation method (P-1))
Use lower layer reflection preventing film to form agent (trade name " ARC29A ", daily output chemical company system), form the lower layer reflection preventing film of thickness 77nm at 8 inches silicon chip surfaces.Through being spin-coated on the surface applied radiation sensitive resin composition of this substrate, on heating plate, at 100 ℃ of SB (soft baking) that carried out for 60 seconds, form the photoresist film of thickness 120nm.
Use full field reduced projection exposure device (trade name " NSRS306C ", NIKON corporate system), be situated between by mask pattern this photoresist film exposure.Then, under 100 ℃, carry out the postexposure bake (PEB) in 60 seconds, utilize 2.38% tetramethylammonium hydroxide aqueous solution (below be also referred to as " the TMAH WS ") then, developed for 60 seconds down, wash, drying, form the resist pattern of eurymeric at 25 ℃.Should explain that the resist pattern of this eurymeric forms 1: 1 the Line&Space of the live width 90nm that the mask of usefulness forms for 1: 1 the Line&Space by target size 90nm of being situated between.The survey of the resist pattern that is formed by this method is long, and what use is scanning electron microscope (trade name " S9260A ", the HIGHTECHNOLOGIES of Hitachi corporate system).With this pattern formation method as (P-1).
(pattern formation method (P-2))
Be identically formed on 12 inches silicon chips of lower layer reflection preventing film with pattern formation method (P-1), utilizing radiation sensitive resin composition to form the photoresist film of thickness 75nm, under 100 ℃, carrying out the soft baking (SB) in 60 seconds.Then, upper layer film formation is spun on the photoresist film of formation with composition (H), carries out PB (90 ℃, 60 seconds), thereby form the upper layer film of thickness 90nm.Then, use ArF PRK liquid immersion exposure apparatus (trade name " NSRS610C ", NIKON corporate system), under the condition of NA=1.3, ratio=0.800, Annular, be situated between and make public by mask pattern.After the exposure, under 95 ℃, carry out the postexposure bake (PEB) in 60 seconds.Then, utilize 2.38% the TMAH WS to develop, wash, drying, form the resist pattern of eurymeric.Should explain that the resist pattern of this eurymeric is for being situated between by being used to form 1: 1 the Line&Space that target size is the live width 50nm that forms of the mask of line 50nm spacing 100nm.The survey of the resist pattern that is formed by this method is long, and what use is scanning electron microscope (trade name " CG-4000 ", the HIGH TECHNOLOGIES of Hitachi corporate system).
(pattern formation method (P-3))
Be identically formed on 12 inches silicon chips of lower layer reflection preventing film with pattern formation method (P-1), utilizing the photoresist film of radiation sensitive resin composition formation thickness 75nm, under 100 ℃, carrying out the SB in 60 seconds.Then, use above-mentioned ArF PRK liquid immersion exposure apparatus, under the condition of NA=1.3, ratio=0.800, Annular, be situated between by mask pattern this photoresist film exposure.After the exposure, under 85 ℃, carry out postexposure bake in 60 seconds (PEB).Then, utilize 2.38% the TMAH WS to develop, wash, drying, form the resist pattern of eurymeric.Should explain that the resist pattern of this eurymeric is for being situated between by being used to form 1: 1 the Line&Space that target size is the live width 50nm that forms of the mask of line 50nm spacing 100nm.The survey of the resist pattern that is formed by this method is long, and what use is scanning electron microscope (" CG-4000 ", the HIGH TECHNOLOGIES of Hitachi corporate system).
Each is estimated and carries out through following method.The result who obtains is as shown in table 2.
[sensitivity]
Under the situation of above-mentioned pattern formation method (P-1), the live width that the mask by 1 of size 90nm: 1Line&Space of being situated between forms will form the exposure (mJ/cm of 1 of live width 90nm: 1Line&Space 2) as optimum exposure, with this optimum exposure (mJ/cm 2) as " sensitivity ".Likewise, under above-mentioned pattern formation method (P-2) and situation (P-3), the live width that the mask by 1 of size 50nm: 1Line&Space of being situated between forms will form the exposure (mJ/cm of 1 of live width 50nm: 1Line&Space 2) as optimum exposure, with this optimum exposure (mJ/cm 2) as " sensitivity ".
[exposure latitude (Exposure Latitude:EL)]
Under the situation of above-mentioned pattern formation method (P-1), with the 1L/1S mask pattern exploring that utilizes 90nm and pattern dimension reach mask design size ± 10% in the time exposure with respect to the ratio of optimum exposure as exposure latitude (EL).Likewise; Under above-mentioned pattern formation method (P-2) and situation (P-3), with the 1L/1S mask pattern exploring that utilizes 50nm and pattern dimension reach mask design size ± 10% in the time exposure with respect to the ratio of optimum exposure as exposure latitude (EL).The numerical value of this value is the bigger the better.Should explain that what the observation of pattern dimension was used is above-mentioned scanning electron microscope.
[MEEF]
Use above-mentioned scanning electron microscope, be determined at the pattern dimension that under the situation of utilizing above-mentioned pattern formation method (P-1), gets under the optimum exposure with 3 kinds of mask size (85.0nmL/170nmP, 90.0nmL/180nmP, 95.0nmL/190nmP) exploring.It is measured the result be mask size with the transverse axis, be that live width is charted with the longitudinal axis, obtain the slope of curve map through least square method.Identical ground is determined at and utilizes the pattern dimension that gets with 3 kinds of mask size (46.0nmL/92nmP, 50.0nmL/100nmP, 54.0nmL/108nmP) exploring under above-mentioned pattern formation method (P-2) and the situation (P-3).It is measured the result be mask size with the transverse axis, be that live width is charted with the longitudinal axis, obtain the slope of curve map through least square method.With this slope as MEEF.The numerical value of this value is more little good more.
[table 2]
Figure BDA0000142942810000411
Utilizability in the industry
It is the photoetching material of light source that radiation sensitive resin composition of the present invention can be suitable as with KrF PRK and ArF PRK.In addition, can also tackle immersion exposure.

Claims (7)

1. a radiation sensitive resin composition is characterized in that, contains:
(A) have the compound of the structure that the group of following formula (1) expression combines with nitrogen-atoms,
(B) have resin that acid dissociation property dissolution inhibiting group and the effect alkali-soluble through acid increase and
(C) radiation-sensitive acid producing agent;
Figure FDA0000142942800000011
In the formula (1), Y is for by following formula (i) expression and carbon number being 5～20 1 valency group, the binding site of " * " expression and nitrogen-atoms;
In the formula (i), R 1, R 2And R 3Be straight chain shape or the alkyl of branched or 1 valency ester ring type alkyl, the perhaps R of carbon number 4～12 of carbon number 1～4 independently of one another 1And R 2Mutually combining and forming carbon number with the carbon atom that they combined is 4～12 divalent ester ring type alkyl, the binding site of " * " expression and oxygen atom.
2. radiation sensitive resin composition according to claim 1, wherein, (A) compound is represented by following formula (1-1),
Figure FDA0000142942800000013
In the formula (1-1), the definition of Y is identical with following formula (1), R 4And R 5Be alkyl, the ester ring type alkyl of 1 valency, aryl or aralkyl, the perhaps R of hydrogen atom, straight chain shape or branched independently of one another 4And R 5Mutually combining and forming carbon number with the nitrogen-atoms that they combined is 4～20 divalent hetero ring type group.
3. radiation sensitive resin composition according to claim 1, wherein, the Y in the following formula (1) is a tertiary pentyl.
4. radiation sensitive resin composition according to claim 1, wherein, (B) resin has the repetitive of following formula (3) expression,
In the formula (3), R is hydrogen atom or methyl, R 6, R 7And R 8Be straight chain shape or the alkyl of branched or 1 valency ester ring type alkyl, the perhaps R of carbon number 4～20 of carbon number 1～4 independently of one another 6, R 7And R 8In 2 to mutually combine and form carbon number with the carbon atom that they combined be 4～20 divalent ester ring type alkyl.
5. radiation sensitive resin composition according to claim 1, wherein, (B) resin has the repetitive that contains at least a kind of skeleton from lactone skeleton and cyclic carbonate skeleton, selecting.
6. a compound is characterized in that, has the structure that the group of following formula (I) expression combines with nitrogen-atoms, and molecular weight is below 3000,
In the formula (I), the binding site of " * " expression and nitrogen-atoms.
7. compound according to claim 6, it is by following formula (I-1) expression,
Figure FDA0000142942800000023
In the formula (I-1), R 4And R 5Be alkyl, the ester ring type alkyl of 1 valency, aryl or aralkyl, the perhaps R of hydrogen atom, straight chain shape or branched independently of one another 4And R 5Mutually combining and forming carbon number with the nitrogen-atoms that they combined is 4～20 divalent hetero ring type group.
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